skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode

Abstract

Defects are important features in two-dimensional (2D) materials that have a strong influence on their chemical and physical properties. Through the enhanced chemical reactivity at defect sites (point defects, line defects, etc.), one can selectively functionalize 2D materials via chemical reactions and thereby tune their physical properties. We demonstrate the selective atomic layer deposition of LiF on defect sites of h-BN prepared by chemical vapor deposition. The LiF deposits primarily on the line and point defects of h-BN, thereby creating seams that hold the h-BN crystallites together. The chemically and mechanically stable hybrid LiF/h-BN film successfully suppresses lithium dendrite formation during both the initial electrochemical deposition onto a copper foil and the subsequent cycling. In conclusion, the protected lithium electrodes exhibit good cycling behavior with more than 300 cycles at relatively high coulombic efficiency (>95%) in an additive-free carbonate electrolyte.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]
  1. Stanford Univ., Stanford, CA (United States)
  2. Bosch Research and Technology Center North America, Palo Alto, CA (United States)
  3. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1419315
Grant/Contract Number:
award338316; Battery Materials Research (BMR) & Battery 500 Consortium program; award338315; (BERN) Grant No. 03.25.SS.15; AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 3; Journal Issue: 11; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Xie, Jin, Liao, Lei, Gong, Yongji, Li, Yanbin, Shi, Feifei, Pei, Allen, Sun, Jie, Zhang, Rufan, Kong, Biao, Subbaraman, Ram, Christensen, Jake, and Cui, Yi. Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode. United States: N. p., 2017. Web. doi:10.1126/sciadv.aao3170.
Xie, Jin, Liao, Lei, Gong, Yongji, Li, Yanbin, Shi, Feifei, Pei, Allen, Sun, Jie, Zhang, Rufan, Kong, Biao, Subbaraman, Ram, Christensen, Jake, & Cui, Yi. Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode. United States. doi:10.1126/sciadv.aao3170.
Xie, Jin, Liao, Lei, Gong, Yongji, Li, Yanbin, Shi, Feifei, Pei, Allen, Sun, Jie, Zhang, Rufan, Kong, Biao, Subbaraman, Ram, Christensen, Jake, and Cui, Yi. 2017. "Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode". United States. doi:10.1126/sciadv.aao3170. https://www.osti.gov/servlets/purl/1419315.
@article{osti_1419315,
title = {Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode},
author = {Xie, Jin and Liao, Lei and Gong, Yongji and Li, Yanbin and Shi, Feifei and Pei, Allen and Sun, Jie and Zhang, Rufan and Kong, Biao and Subbaraman, Ram and Christensen, Jake and Cui, Yi},
abstractNote = {Defects are important features in two-dimensional (2D) materials that have a strong influence on their chemical and physical properties. Through the enhanced chemical reactivity at defect sites (point defects, line defects, etc.), one can selectively functionalize 2D materials via chemical reactions and thereby tune their physical properties. We demonstrate the selective atomic layer deposition of LiF on defect sites of h-BN prepared by chemical vapor deposition. The LiF deposits primarily on the line and point defects of h-BN, thereby creating seams that hold the h-BN crystallites together. The chemically and mechanically stable hybrid LiF/h-BN film successfully suppresses lithium dendrite formation during both the initial electrochemical deposition onto a copper foil and the subsequent cycling. In conclusion, the protected lithium electrodes exhibit good cycling behavior with more than 300 cycles at relatively high coulombic efficiency (>95%) in an additive-free carbonate electrolyte.},
doi = {10.1126/sciadv.aao3170},
journal = {Science Advances},
number = 11,
volume = 3,
place = {United States},
year = 2017,
month =
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:
  • Lithium metal is considered to be the most promising anode for next-generation batteries due to its high energy density of 3840 mAh g–1. However, the extreme reactivity of the Li surface can induce parasitic reactions with solvents, contamination, and shuttled active species in the electrolyte, reducing the performance of batteries employing Li metal anodes. One promising solution to this issue is application of thin chemical protection layers to the Li metal surface. Using a custom-made ultrahigh vacuum integrated deposition and characterization system, we demonstrate atomic layer deposition (ALD) of protection layers directly on Li metal with exquisite thickness control. Wemore » demonstrate as a proof-of-concept that a 14 nm thick ALD Al2O3 layer can protect the Li surface from corrosion due to atmosphere, sulfur, and electrolyte exposure. Using Li–S battery cells as a test system, we demonstrate an improved capacity retention using ALD-protected anodes over cells assembled with bare Li metal anodes for up to 100 cycles.« less
  • Here, developing advanced technologies to stabilize positive electrodes of lithium ion batteries under high-voltage operation is becoming increasingly important, owing to the potential to achieve substantially enhanced energy density for applications such as portable electronics and electrical vehicles. Here, we deposited chemically inert and ionically conductive LiAlO 2 interfacial layers on LiCoO 2 electrodes using the atomic layer deposition technique. During prolonged cycling at high-voltage, the LiAlO 2 coating not only prevented interfacial reactions between the LiCoO 2 electrode and electrolyte, as confirmed by electrochemical impedance spectroscopy and Raman characterizations, but also allowed lithium ions to freely diffuse into LiCoOmore » 2 without sacrificing the power density. As a result, a capacity value close to 200 mA·h·g –1 was achieved for the LiCoO 2 electrodes with commercial level loading densities, cycled at the cut-off potential of 4.6 V vs. Li +/Li for 50 stable cycles; this represents a 40% capacity gain, compared with the values obtained for commercial samples cycled at the cut-off potential of 4.2 V vs. Li +/Li.« less
    Cited by 1
  • We present that lithium metal is a highly desirable anode material for lithium batteries due to its extremely high theoretical capacity (3860 mA h g -1), low potential (-3.04 V versus standard hydrogen electrode), and low density (0.534 g cm -3). However, dendrite growth during cycling and low coulombic efficiency, resulting in safety hazards and fast battery fading, are huge barriers to commercialization. Herein, we used atomic layer deposition (ALD) to prepare conformal, ultrathin aluminum oxide coatings on lithium. We investigated the growth mechanism during Al 2O 3 ALD on lithium by in situ quartz crystal microbalance and found largermore » growth than expected during the initial cycles. We also discovered that the ALD Al 2O 3 enhances the wettability of the Li surface towards both carbonate and ether electrolytes, leading to uniform and dense SEI formation and reduced electrolyte consumption during battery operation. Scanning electron microscopy verified that the bare Li surfaces become rough and dendritic after electrochemical cycling, whereas the ALD Al 2O 3 coated Li surfaces remain smooth and uniform. Analysis of the Li surfaces after cycling using X-ray photoelectron spectroscopy and in situ transmission electron microscopy revealed that the ALD Al 2O 3 coating remains intact during electrochemical cycling, and that Li ions diffuse through the coating and deposit on the underlying Li. Coin cell testing demonstrated more than two times longer cycling life for the ALD Al 2O 3 protected Li, and a coulombic efficiency as high as ~98% at a practical current rate of 1 mA cm -2. More significantly, when the electrolyte volume was reduced from 20 to 5 μL, the stabilizing effect of the ALD coating became even more pronounced and the cycling life was around four times longer. Finally, these results indicate that ALD Al 2O 3 coatings are a promising strategy to stabilize Li anodes for high performance energy storage devices such as Li–S batteries.« less